Cable-type secondary battery

ABSTRACT

The present disclosure provides a cable-type secondary battery, comprising: an inner electrode; a separation layer surrounding the outer surface of the inner electrode to prevent a short circuit between electrodes; and a sheet-form outer electrode spirally wound to surround the separation layer or the inner electrode.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of International Application No.PCT/KR2014/004043 filed on May 7, 2014, which claims priority under 35USC 119(a) to Korean Patent Application No. 10-2013-0051562 filed in theRepublic of Korea on May 7, 2013, and Korean Patent Application No.10-2014-0054276 filed in the Republic of Korea on May 7, 2014, thedisclosure of which is incorporated herein by reference.

TECHNICAL FIELD

The present disclosure relates to a cable-type secondary battery whichcan freely change in shape, and more specifically to a cable-typesecondary battery constructed to be prevented from the release of anelectrode active material layer and to have improved electrodeflexibility.

BACKGROUND ART

Secondary batteries are devices capable of storing energy in chemicalform and of converting into electrical energy to generate electricitywhen needed. The secondary batteries are also referred to asrechargeable batteries because they can be recharged repeatedly. Commonsecondary batteries include lead accumulators, NiCd batteries, NiMHaccumulators, Li-ion batteries, Li-ion polymer batteries, and the like.When compared with disposable primary batteries, not only are thesecondary batteries more economically efficient, they are also moreenvironmentally friendly.

Secondary batteries are currently used in applications requiring lowelectric power, for example, equipment to start vehicles, mobiledevices, tools, uninterruptible power supplies, and the like. Recently,as the development of wireless communication technologies has beenleading to the popularization of mobile devices and even to themobilization of many kinds of conventional devices, the demand forsecondary batteries has been dramatically increasing. Secondarybatteries are also used in environmentally friendly next-generationvehicles such as hybrid vehicles and electric vehicles to reduce thecosts and weight and to increase the service life of the vehicles.

Generally, secondary batteries have a cylindrical, prismatic, or pouchshape. This is associated with a fabrication process of the secondarybatteries in which an electrode assembly composed of an anode, acathode, and a separator is mounted in a cylindrical or prismatic metalcasing or a pouch-shaped casing of an aluminum laminate sheet, and inwhich the casing is filled with electrolyte. Because a predeterminedmounting space for the electrode assembly is necessary in this process,the cylindrical, prismatic or pouch shape of the secondary batteries isa limitation in developing various shapes of mobile devices.Accordingly, there is a need for secondary batteries of a new structurethat are easily adaptable in shape.

To fulfill this need, suggestions have been made to develop cable-typebatteries having a very high ratio of length to cross-sectionaldiameter. The cable-type batteries are easy in shape variation, whilebeing subject to stress due to external force for the shape variation.Also, the electrode active material layer of cable-type batteries may bereleased by rapid volume expansion during charging and dischargingprocesses. From these reasons, the capacity of the batteries may bereduced and the cycle life characteristics thereof may be deteriorated.

Such a problem may be solved in a certain degree by increasing theamount of a binder used in the electrode active material layer toprovide flexibility during bending or twisting. However, the increase ofa binder amount in the electrode active material layer causes anelectrode resistance rise to deteriorate battery performances. Also,when intense external forces are applied, for example, in the case thatelectrodes are completely folded, the release of the electrode activematerial layer cannot be prevented even though the amount of a binderbecomes increased. Therefore, this method is insufficient to solve suchproblems.

SUMMARY OF THE DISCLOSURE

The present disclosure is designed to solve the problems of the relatedart, and therefore the present disclosure is directed to providing acable-type battery which can be mitigated from crack generation in anelectrode active material layer by external forces, and also can beprevented from the release of the electrode active material layer from acurrent collector even if severe cracks are present.

In accordance with one aspect of the present disclosure, there isprovided a cable-type secondary battery, comprising: an inner electrode;a separation layer surrounding the outer surface of the inner electrodeto prevent a short circuit between electrodes; and a sheet-form outerelectrode spirally wound to surround the separation layer or the innerelectrode .

The separation layer may be laminated on the outer electrode to form anassembly of separation layer-outer electrode, and the assembly ofseparation layer-outer electrode may be spirally wound to surround theinner electrode.

Meanwhile, the sheet-form outer electrode may be in the form of auniaxially extended strip.

The sheet-form outer electrode may be spirally wound so that it is notoverlapped in its width or overlapped in its width.

The sheet-form outer electrode may comprise an outer current collectorand an outer electrode active material layer formed on one surface ofthe outer current collector.

Also, the sheet-form outer electrode may further comprise a first poroussupporting layer formed on the outer electrode active material layer.

In addition, the sheet-form outer electrode may further comprise aporous coating layer formed on the first porous supporting layer andcomprising a mixture of inorganic particles and a binder polymer.

Moreover, the sheet-form outer electrode may further comprise a secondsupporting layer formed on another surface of the outer currentcollector.

Additionally, the sheet-form outer electrode may further comprise aconductive layer between the outer electrode active material layer andthe first supporting layer, the conductive layer comprising a conductivematerial and a binder.

Meanwhile, the inner electrode may comprise one or more inner currentcollector and an inner electrode active material layer formed on asurface of the inner current collector.

The inner electrode may be a hollow structure whose central part isempty.

The inner current collector comprised in the inner electrode may be oneor more wires being spirally wound, one or more sheets being spirallywound, or two or more wires being spirally crossed with each other.

Also, the inner electrode may be provided with a core of inner currentcollector, a core for supplying lithium ions, which comprises anelectrolyte, or a filling core therein.

The core for supplying lithium ions may further comprise a gel polymerelectrolyte and a support, or may further comprise a liquid electrolyteand a porous carrier.

Meanwhile, the inner electrode may have a structure that the innerelectrode active material layer is formed on the whole surface of theinner current collector, or a structure that the inner electrode activematerial layer is formed to surround the outer surface of the innercurrent collector.

Also, the inner electrode may further comprise a polymer supportinglayer formed on a surface of the inner electrode active material layer.

The polymer supporting layer may be a porous layer having a pore size of0.01 to 10 μm and a porosity of 5 to 95%.

Also, the polymer supporting layer may comprise a linear polymer withpolarity, an oxide-based linear polymer or a mixture thereof.

The linear polymer with polarity may be selected from the groupconsisting of polyacrylonitrile, polyvinyl chloride, polyvinylidenefluoride (PVDF), polyvinylidene fluoride-co-hexafluoro propylene,polyvinylidene fluoride-co-trichloroethylene, polyethylene imine,polymethyl methacrylate, polybutyl acrylate, polyvinylpyrrolidone,polyvinylacetate, polyethylene-co-vinyl acetate, polyarylate,poly-p-phenylene terephthalamide and a mixture thereof.

The oxide-based linear polymer may be selected from the group consistingof polyethylene oxide, polypropylene oxide, polyoxymethylene,polydimethylsiloxane and a mixture thereof.

The inner current collector may be made of stainless steel, aluminum,nickel, titanium, sintered carbon, or copper; stainless steel treatedwith carbon, nickel, titanium or silver on the surface thereof; analuminum-cadmium alloy; a non-conductive polymer treated with aconductive material on the surface thereof; or a conductive polymer.

The conductive material used in the inner current collector may beselected from the group consisting of polyacetylene, polyaniline,polypyrrole, polythiophene, polysulfurnitride, indium tin oxide (ITO),silver, palladium, nickel and a mixture thereof. The conductive polymerused in the inner current collector may be selected from the groupconsisting of polyacetylene, polyaniline, polypyrrole, polythiophene,polysulfurnitride and a mixture thereof.

Meanwhile, the outer current collector may be in the form of a mesh.

Also, at least one of the inner current collector and the outer currentcollector may further comprise a primer coating layer consisting of aconductive material and a binder.

The outer current collector may have a plurality of recesses on at leastone surface thereof.

The plurality of recesses may be continuously patterned orintermittently patterned.

In addition, the outer current collector may be made of stainless steel,aluminum, nickel, titanium, sintered carbon, or copper; stainless steeltreated with carbon, nickel, titanium or silver on the surface thereof;an aluminum-cadmium alloy; a non-conductive polymer treated with aconductive material on the surface thereof; a conductive polymer; ametal paste comprising metal powders of Ni, Al, Au, Ag, Pd/Ag, Cr, Ta,Cu, Ba or ITO; or a carbon paste comprising carbon powders of graphite,carbon black or carbon nanotube.

Meanwhile, the first supporting layer may be a mesh-form porous membraneor a non-woven fabric.

The first supporting layer may be made of any one selected from thegroup consisting of high-density polyethylene, low-density polyethylene,linear low-density polyethylene, ultra-high molecular weightpolyethylene, polypropylene, polyethylene terephthalate, polybutyleneterephthalate, polyester, polyacetal, polyamide, polycarbonate,polyimide, polyetheretherketone, polyethersulfone, polyphenylene oxide,polyphenylene sulfide, polyethylene naphthalate, and a mixture thereof.

Also, the first supporting layer may further comprise a conductivematerial-coating layer having a conductive material and a binder on thetop surface thereof.

In the conductive material-coating layer, the conductive material andthe binder may be present in a weight ratio of 80:20 to 99:1.

Meanwhile, the second supporting layer may be a polymer film which maybe made of any one selected from the group consisting of polyolefin,polyester, polyimide, polyamide and a mixture thereof.

The conductive layer may be formed from a mixture of the conductivematerial and the binder in a weight ratio of 1:10 to 8:10.

Also, the conductive layer may be a porous layer having a pore size of0.01 to 5 μm and a porosity of 5 to 70%.

The conductive material may comprise any one selected from the groupconsisting of carbon black, acetylene black, ketjen black, carbon fiber,carbon nanotube, graphene and a mixture thereof.

The binder may be selected from the group consisting of polyvinylidenefluoride (PVDF), polyvinylidene fluoride-co-hexafluoro propylene,polyvinylidene fluoride-co-trichloroethylene, polybutyl acrylate,polymethyl methacrylate, polyacrylonitrile, polyvinylpyrrolidone,polyvinylacetate, polyethylene-co-vinyl acetate, polyethylene oxide,polyarylate, cellulose acetate, cellulose acetate butyrate, celluloseacetate propionate, cyanoethylpullulan, cyanoethylpolyvinylalcohol,cyanoethylcellulose, cyanoethylsucrose, pullulan, carboxyl methylcellulose, styrene-butadiene rubber, acrylonitrile-styrene-butadienecopolymer, polyimide and a mixture thereof.

The electrolyte which is used in the core for supplying lithium ions maybe selected from a non-aqueous electrolyte solution using ethylenecarbonate (EC), propylene carbonate (PC), butylenes carbonate (BC),vinylene carbonate (VC), diethyl carbonate (DEC), dimethyl carbonate(DMC), ethyl methyl carbonate (EMC), methyl formate (MF),γ-butyrolactone (γ-BL), sulfolane, methyl acetate (MA) or methylpropionate (MP); a gel polymer electrolyte using PEO, PVdF, PVdF-HFP,PMMA, PAN, or PVAc; and a solid electrolyte using PEO, polypropyleneoxide (PPO), polyether imine (PEI), polyethylene sulphide (PES), orpolyvinyl acetate (PVAc).

The electrolyte may further comprise a lithium salt which may beselected from LiCl, LiBr, LiI, LiClO₄, LiBF₄, LiB₁₀Cl₁₀, LiPF₆,LiCF₃SO₃, LiCF₃CO₂, LiAsF₆, LiSbF₆, LiAlCl₄, CH₃SO₃Li, CF₃SO₃Li,(CF₃SO₂)₂NLi, lithium chloroborate, lower aliphatic lithium carbonate,lithium tetraphenylborate, and a mixture thereof.

Meanwhile, the inner electrode may be an anode or a cathode, and theouter electrode may be a cathode or an anode corresponding to the innerelectrode.

When the inner electrode is an anode and the outer electrode is acathode, the inner electrode active material may comprise any oneselected from the group consisting of natural graphite, artificialgraphite, or carbonaceous material; lithium-titanium complex oxide(LTO), and metals (Me) including Si, Sn, Li, Zn, Mg, Cd, Ce, Ni and Fe;alloys of the metals; an oxide (MeOx) of the metals; a complex of themetals and carbon; and a mixture thereof, and the outer electrode activematerial may comprise any one selected from the group consisting ofLiCoO₂, LiNiO₂, LiMn₂O₄, LiCoPO₄, LiFePO₄, LiNiMnCoO₂,LiNi_(1-x-y-z)Co_(x)M1_(y)M2_(z)O₂ (wherein M1 and M2 are eachindependently selected from the group consisting of Al, Ni, Co, Fe, Mn,V, Cr, Ti, W, Ta, Mg and Mo, and x, y and z are each independently anatomic fraction of oxide-forming elements, in which 0≦x<0.5, 0≦y<0.5,0≦z<0.5, and x+y+z≦1), and a mixture thereof.

Alternatively, when the inner electrode is a cathode and the outerelectrode is an anode, the inner electrode active material may compriseany one selected from the group consisting of LiCoO₂, LiNiO₂, LiMn₂O₄,LiCoPO₄, LiFePO₄, LiNiMnCoO₂, LiNi_(1-x-y-z)Co_(x)M1_(y)M2_(z)O₂(wherein M1 and M2 are each independently selected from the groupconsisting of Al, Ni, Co, Fe, Mn, V, Cr, Ti, W, Ta, Mg and Mo, and x, yand z are each independently an atomic fraction of oxide-formingelements, in which 0≦x<0.5, 0≦y<0.5, 0≦z<0.5, and x+y+z≦1), and amixture thereof, and the outer electrode active material may compriseany one selected from the group consisting of natural graphite,artificial graphite, or carbonaceous material; lithium-titanium complexoxide (LTO), and metals (Me) including Si, Sn, Li, Zn, Mg, Cd, Ce, Niand Fe; alloys of the metals; an oxide (MeOx) of the metals; a complexof the metals and carbon; and a mixture thereof.

Meanwhile, the separation layer may be an electrolyte layer or aseparator.

The electrolyte layer may comprise an electrolyte selected from a gelpolymer electrolyte using PEO, PVdF, PMMA, PVdF-HFP, PAN, or PVAc; and asolid electrolyte using PEO, polypropylene oxide (PPO), polyether imine(PEI), polyethylene sulphide (PES), or polyvinyl acetate (PVAc).

The electrolyte layer may further comprise a lithium salt, which may beselected from the group consisting of LiCl, LiBr, LiI, LiClO₄, LiBF₄,LiB₁₀Cl₁₀, LiPF₆, LiCF₃SO₃, LiCF₃CO₂, LiAsF₆, LiSbF₆, LiAlCl₄, CH₃SO₃Li,CF₃SO₃Li, (CF₃SO₂)₂NLi, lithium chloroborate, lower aliphatic lithiumcarbonate, lithium tetraphenylborate, and a mixture thereof.

The separator may be a porous polymer substrate made of apolyolefin-based polymer selected from the group consisting of ethylenehomopolymers, propylene homopolymers, ethylene-butene copolymers,ethylene-hexene copolymers, and ethylene-methacrylate copolymers; aporous polymer substrate made of a polymer selected from the groupconsisting of polyesters, polyacetals, polyamides, polycarbonates,polyimides, polyether ether ketones, polyether sulfones, polyphenyleneoxides, polyphenylene sulfides and polyethylene naphthalates; a poroussubstrate made of a mixture of inorganic particles and a binder polymer;or a separator having a porous coating layer formed on at least onesurface of the porous polymer substrate and comprising inorganicparticles and a binder polymer.

Further, in accordance with another aspect of the present invention,there is provided a cable-type secondary battery, comprising: a core forsupplying lithium ions, which comprise an electrolyte; an innerelectrode comprising one or more wire-form inner current collector whichis wound to surround the outer surface of the core for supplying lithiumions, and an inner electrode active material layer formed on a surfaceof the wire-form inner current collector; a separation layer surroundingthe outer surface of the inner electrodes to prevent a short circuitbetween electrodes; and a sheet-form outer electrode surrounding theouter surface of the separation layer, wherein the outer electrodecomprises an outer current collector, an outer electrode active materiallayer formed on one surface of the outer current collector, a conductivelayer formed on the outer electrode active material layer and comprisinga conductive material and a binder, a first porous supporting layerformed on the conductive layer, and a second supporting layer formed onanother surface of the outer current collector.

The outer electrode may be spirally wound to surround the separationlayer.

In accordance with still another aspect of the present disclosure, thereis provided a cable-type secondary battery, comprising: two or moreinner electrodes arranged in parallel to each other; a separation layersurrounding the outer surface of the inner electrodes to prevent a shortcircuit between electrodes; and a sheet-form outer electrode surroundingthe outer surface of the separation layer.

The outer electrode may be spirally wound to surround the separationlayer.

In accordance with still another aspect of the present disclosure, thereis provided a cable-type secondary battery, comprising: two or morecores for supplying lithium ions, which comprise an electrolyte; two ormore inner electrodes arranged in parallel to each other, each innerelectrode comprising one or more wire-form inner current collector whichis wound to surround the outer surface of each core for supplyinglithium ions, and an inner electrode active material layer formed on asurface of the wire-form inner current collector; a separation layersurrounding the outer surface of the inner electrodes to prevent a shortcircuit between electrodes; and a sheet-form outer electrode surroundingthe outer surface of the separation layer, wherein the outer electrodecomprises an outer current collector, an outer electrode active materiallayer formed on one surface of the outer current collector, a conductivelayer formed on the outer electrode active material layer and comprisinga conductive material and a binder, a first porous supporting layerformed on the conductive layer, and a second supporting layer formed onanother surface of the outer current collector.

The outer electrode may be spirally wound to surround the separationlayer.

Also, the inner current collector comprised in the inner electrode maybe one or more wires being spirally wound, or one or more sheets beingspirally wound.

Thus, the cable-type secondary battery of the present disclosure hassupporting layers on both surfaces of a sheet-form outer electrode toexhibit surprisingly improved electrode flexibility.

The supporting layers act as a buffer to reduce crack generation in anelectrode active material layer even though the amount of a binder in anelectrode active material layer is not raised. Thereby, the release ofthe electrode active material layer from a current collector can beprevented.

From this, battery capacity can be prevented from its decrease and thecycle life characteristic of batteries can be improved.

Also, the cable-type secondary battery of the present disclosure has aconductive layer on the top surface of an outer electrode activematerial layer to provide an increased conductivity.

Further, the cable-type secondary battery of the present disclosure hasa porous supporting layer to allow good introduction of an electrolytesolution in an electrode active material layer, and also the electrolytesolution can be impregnated into the pores of the porous supportinglayer to inhibit a resistance rise in the battery, thereby preventingthe deterioration of battery performances.

BRIEF DESCRIPTION OF THE DRAWINGS

Other objects and aspects of the present disclosure will become apparentfrom the following descriptions of the embodiments with reference to theaccompanying drawings in which:

FIG. 1 is a perspective view schematically showing a cable-typesecondary battery having a wire-form outer current collector accordingto a comparative example of the present disclosure.

FIG. 2 is a perspective view schematically showing a cable-typesecondary battery having a sheet-form outer current collector accordingto one embodiment of the present disclosure.

FIG. 3 is a perspective view schematically showing a cable-typesecondary battery having a sheet-form outer current collector accordingto another embodiment of the present disclosure.

FIG. 4 is a schematic view showing a cross-section of a sheet-form outercurrent collector according to one embodiment of the present disclosure.

FIG. 5 is a perspective view schematically showing a cable-typesecondary battery having a sheet-form outer current collector accordingto another embodiment of the present disclosure.

FIG. 6 shows a surface of a mesh-form current collector according to oneembodiment of the present disclosure.

FIG. 7 schematically shows a surface of a current collector having aplurality of recesses, according to one embodiment of the presentdisclosure.

FIG. 8 schematically shows a surface of a current collector having aplurality of recesses, according to another embodiment of the presentdisclosure.

FIG. 9 schematically shows a sheet-form outer electrode being wound onthe outer surface of a separation layer.

FIG. 10 shows a cross-section of a cable-type secondary battery havingtwo or more inner electrodes according to the present disclosure.

FIG. 11 is a graph showing the cycle life characteristics of cable-typesecondary batteries prepared in the Example and the Comparative Exampleof the present disclosure.

FIG. 12 is a graph showing a capacity change to current density ofcable-type secondary batteries prepared in the Example and theComparative Example of the present disclosure.

FIG. 13 is a graph showing the discharge profile change under severebending conditions of a cable-type secondary battery prepared in theExample of the present disclosure.

EXPLANATION OF REFERENCE NUMERALS

-   10, 100, 200, 300: Cable-type secondary battery-   11, 110, 210, 310: Core for supplying lithium ions-   12, 120, 220, 320: Wire-form Inner current collector-   13, 130, 230, 330: Inner electrode active material layer-   14, 140, 240, 340: Separation layer-   15, 151, 351: Outer current collector-   16, 152, 352: Outer electrode active material layer-   17, 160, 260, 360: Protection coating-   20: Cable-type secondary battery-   21: Inner electrode-   24: Separation layer-   25: Outer electrode-   150, 250, 350: Outer electrode-   153, 253, 353: Conductive layer-   154, 254, 354: First supporting layer-   155, 255, 355: Second supporting layer

DESCRIPTION OF THE PREFERRED EMBODIMENT

Hereinafter, preferred embodiments of the present disclosure will bedescribed in detail with reference to the accompanying drawings. Priorto the description, it should be understood that the terms used in thespecification and the appended claims should not be construed as limitedto general and dictionary meanings, but interpreted based on themeanings and concepts corresponding to technical aspects of the presentdisclosure on the basis of the principle that the inventor is allowed todefine terms appropriately for the best explanation.

Therefore, the description proposed herein is just a preferable examplefor the purpose of illustrations only, not intended to limit the scopeof the disclosure, so it should be understood that other equivalents andmodifications could be made thereto without departing from the spiritand scope of the disclosure.

FIG. 1 shows a cable-type secondary battery having a wire-form outercurrent collector according to a comparative example of the presentdisclosure and FIGS. 2 to 5 schematically show a sheet-form outerelectrode and a cable-type secondary battery having the sheet-form outerelectrode in accordance with one embodiment of the present disclosure.

Referring to FIGS. 1 to 5, a cable-type secondary battery 10 accordingto a comparative example of the present disclosure has a wound wire-formouter current collector 15 and an outer electrode active material layer16 formed by way of dip coating to surround the outer surface of theouter current collector. The outer current collector 15 which isconfigured in the form of a wire provides poor electron transfer duringthe charge and discharge of the battery, as compared with a sheet-formcurrent collector, because a linear resistance is greater than a sheetresistance in the wire form. As a result, the internal resistance of thebattery is raised, thereby deteriorating the rate characteristic of thebattery and leading to the poor life characteristic of the battery evenunder the high rate conditions.

Also, the outer electrode active material layer 16 may be cracked on thesurface thereof, even though the outer electrode active material layeris protected from its shape change by a protection coating underexternal bending or twisting conditions as it is formed by a dip coatingmethod. The generation of cracks may adversely affect electrodeflexibility.

In order to solve this problem, the cable-type secondary battery of thepresent disclosure is configured to have a sheet-form outer electrodesurrounding the outer surface of the separation layer and formed bybeing spirally wound.

That is, a cable-type secondary battery 20 according to one aspect ofthe present disclosure comprises an inner electrode 21; a separationlayer 24 surrounding the outer surface of the inner electrode 21 toprevent a short circuit between electrodes; and a sheet-form outerelectrode 25 surrounding the separation layer 24 or the inner electrode21 and formed by being spirally wound.

The separation layer 24 may be formed by surrounding the outer surfaceof the inner electrode 21 completely.

Also, although not shown in the drawings, the outer electrode may bedisposed in the ouster side of the separation layer and may be spirallywound to surround the separation layer or the inner electrodecompletely.

Furthermore, the separation layer may be laminated on the outerelectrode to form an assembly of separation layer-outer electrode, andthe assembly of separation layer-outer electrode may be spirally woundto surround the inner electrode.

The term ‘spirally’ used herein refers to represent a helix shape thatturns around at a certain area while moving, including general springforms.

In the present disclosure, the outer electrode may comprise an outercurrent collector and an outer electrode active material layer formed onone surface of the outer current collector.

From this, in the assembly of separation layer-outer electrode of thecable-type secondary battery according to one embodiment of the presentdisclosure, the separation layer may come into contact with the outerelectrode active material layer or the outer current collector.

The assembly of separation layer-outer electrode may be integrated byadhesion, for example the assembly of separation layer-outer electrodemay be formed by adhering and integrating the separation layer and theouter electrode through a lamination process by way of roll press.

As will be described below, the sheet-form outer electrode 25 mayfurther comprise a first supporting layer formed on the outer surfacethereof and a second supporting layer formed on another surface thereof,thereby solving crack occurrence on the surface of an outer electrodeactive material layer.

The sheet-form outer electrode may be in the form of a uniaxiallyextended strip.

Also, the sheet-form outer electrode 25 may be spirally wound so that itis not overlapped in its width or overlapped in its width. For example,in order to prevent the deterioration of battery performances, thesheet-form outer electrode 25 may be spirally wound with space withinthe double length of its width so that it is not overlapped.

Alternatively, the sheet-form outer electrode 25 may be spirally woundwhile overlapping in its width. In this case, in order to inhibit anexcessive resistance rise within the battery, the sheet-form outerelectrode 25 may be spirally wound so that the width of its overlappedpart may be within 0.9 folds of the width of the sheet-form outerelectrode 25 itself.

The sheet-form outer electrode may comprise an outer current collectorand an outer electrode active material layer formed on one surface ofthe outer current collector.

Also, the sheet-form outer electrode may further comprise a first poroussupporting layer formed on the outer electrode active material layer.

In addition, the sheet-form outer electrode may further comprise aconductive material coating layer comprising a conductive material and abinder on the first porous supporting layer, and also may furthercomprise a porous coating layer comprising a mixture of inorganicparticles and a binder polymer on the first porous supporting layer.

In the porous coating layer formed from inorganic particles and a binderpolymer, the inorganic particles are bound to each other by the binderpolymer (i.e., the binder polymer connects and immobilizes the inorganicparticles), and also the porous coating layer maintains the state ofbinding with the first supporting layer by the binder polymer, In such aporous coating layer, the inorganic particles are filled in contact witheach other, from which interstitial volumes are formed between theinorganic particles. The interstitial volumes between the inorganicparticles become empty spaces to form pores.

Meanwhile, the sheet-form outer electrode may further comprise a secondsupporting layer formed on another surface of the outer currentcollector.

Also, the sheet-form outer electrode may further comprise a conductivelayer between the outer electrode active material layer and the firstsupporting layer and comprising a conductive material and a binder.

Meanwhile, the inner electrode may comprise one or more inner currentcollector and an inner electrode active material layer formed on asurface of the inner current collector.

The inner electrode may be a hollow structure whose central part isempty.

The inner current collector comprised in the inner electrode may be oneor more wires being spirally wound or one or more sheets being spirallywound.

Alternatively, the inner current collector may be two or more wiresbeing spirally crossed with each other.

Also, the inner electrode may be provided with a core of inner currentcollector therein.

The core of inner current collector may be made of carbon nanotube,stainless steel, aluminum, nickel, titanium, sintered carbon, or copper;stainless steel treated with carbon, nickel, titanium or silver on thesurface thereof; an aluminum-cadmium alloy; a non-conductive polymertreated with a conductive material on the surface thereof; a conductivepolymer.

Alternatively, the inner electrode may be provided with a core forsupplying lithium ions, which comprises an electrolyte therein.

The core for supplying lithium ions may comprise a gel polymerelectrolyte and a support.

Also, the core for supplying lithium ions may comprise a liquidelectrolyte and a porous carrier.

Alternatively, the inner electrode may be provided with a filling coretherein.

The filling core may be made of several materials for improving variousperformances of cable-type batteries, for example polymer resins, rubberand inorganics, besides materials forming the core of inner currentcollector and the core for supplying lithium ions, and also may havevarious forms including wire, fiber, powder, mesh and foam.

Meanwhile, a cable-type secondary battery 100, 200 according to oneembodiment of the present disclosure comprises a core 110, 210 forsupplying lithium ions, which comprises an electrolyte; an innerelectrode, comprising one or more wire-form inner current collector 120,220 which is wound to surround the outer surface of the core 110, 210for supplying lithium ions, and an inner electrode active material layer130, 230 formed on a surface of the wire-form inner current collector120, 220; a separation layer 140, 240 surrounding the outer surface ofthe inner electrode to prevent a short circuit between electrodes; and asheet-form outer electrode 150, 250 surrounding the outer surface of theseparation layer 140, 240, wherein the outer electrode 150, 250comprises an outer current collector 151, an outer electrode activematerial layer 152 formed on one surface of the outer current collector151, a conductive layer 153 formed on the outer electrode activematerial layer 152 and comprising a conductive material and a binder, afirst porous supporting layer 154 formed on the conductive layer 153,and a second supporting layer 155 formed on another surface of the outercurrent collector 151.

The outer electrode may be spirally wound to surround the separationlayer.

The cable-type secondary battery of the present disclosure has ahorizontal cross section of a predetermined shape, a linear structure,which extends in the longitudinal direction, and flexibility, so it canfreely change in shape. The term ‘a predetermined shape’ used herein isnot limited to any particular shape, and refers to any shape that doesnot damage the nature of the present disclosure.

The inner electrode may have a structure that the inner electrode activematerial layer is formed on the whole surface of the inner currentcollector, or a structure that the inner electrode active material layeris formed to surround the outer surface of the inner current collector.

For the structure that the inner electrode active material layer isformed on the whole surface of a wire-form inner current collector, inthe case shown in FIG. 3, the inner electrode active material layer 130may be formed on a surface of one wire-form inner current collector 120before the wire-form inner current collector 120 is wound on the outersurface of the core 110 for supplying lithium ions, and in the caseshown in FIG. 5, the inner electrode active material layer 230 may beformed on a surface of two or more wire-form inner current collectors220 and then two or more wire-form inner current collectors 220 may betogether wound while crossing with each other, which is favorable in theimprovement of battery rate characteristics.

For structure that the inner electrode active material layer is formedto surround the outer surface of a wound wire-form inner currentcollector, a inner current collector may be wound on the outer surfaceof a core for supplying lithium ions, and then an inner electrode activematerial layer is formed to surround the outer surface of the woundwire-form inner current collector.

Also, the inner electrode may further comprise a polymer supportinglayer formed on a surface of the inner electrode active material layer.

In the case that the inner electrode active material layer furthercomprises a polymer supporting layer on a surface thereof, in accordancewith one embodiment of the present disclosure, although the innerelectrode is in the form of a wound wire, it is possible to preventcrack occurrence even when the cable-type secondary battery is bent byexternal force. Thereby, the release of the inner electrode activematerial layer can be prevented to minimize the deterioration of batteryperformances. Furthermore, the polymer supporting layer may have aporous structure which allows good introduction of an electrolytesolution in the inner electrode active material layer, therebypreventing an electrode resistance rise.

In the present disclosure, the polymer supporting layer may comprise alinear polymer with polarity, an oxide-based linear polymer or a mixturethereof.

The linear polymer with polarity may be selected from the groupconsisting of polyacrylonitrile, polyvinyl chloride, polyvinylidenefluoride (PVDF), polyvinylidene fluoride-co-hexafluoro propylene,polyvinylidene fluoride-co-trichloroethylene, polyethylene imine,polymethyl methacrylate, polybutyl acrylate, polyvinylpyrrolidone,polyvinylacetate, polyethylene-co-vinyl acetate, polyarylate,poly-p-phenylene terephthalamide and a mixture thereof.

The oxide-based linear polymer may be selected from the group consistingof polyethylene oxide, polypropylene oxide, polyoxymethylene,polydimethylsiloxane and a mixture thereof.

Also, the polymer supporting layer may be a porous layer having a poresize of 0.01 to 10 μm and a porosity of 5 to 95%.

Such a porous structure of the polymer supporting layer may be formed byphase separation or phase change using a non-solvent during itspreparation.

For example, polyvinylidene fluoride-co-hexafluoro propylene as apolymer is added to acetone used as a solvent to obtain a solutionhaving 10 wt % of solids. To the solution obtained, water or ethanol asa non-solvent is added in an amount of 2 to 10 wt % to formphase-separated parts of the non-solvent and the polymer. Among these,the parts of the non-solvent become pores. Accordingly, the size ofpores can be controlled depending on the solubility of the non-solventand the polymer and the amount of the non-solvent.

Meanwhile, the wire-form inner current collector 120, 220 is preferablymade of stainless steel, aluminum, nickel, titanium, sintered carbon, orcopper; stainless steel treated with carbon, nickel, titanium or silveron the surface thereof; an aluminum-cadmium alloy; a non-conductivepolymer treated with a conductive material on the surface thereof; or aconductive polymer.

Such a current collector serves to collect electrons generated byelectrochemical reaction of the active material or to supply electronsrequired for the electrochemical reaction. In general, the currentcollector is made of a metal such as copper or aluminum. Especially,when the current collector is made of a non-conductive polymer treatedwith a conductive material on the surface thereof or a conductivepolymer, the current collector has a relatively higher flexibility thanthe current collector made of a metal such as copper or aluminum. Also,a polymer current collector may be used instead of the metal currentcollector to reduce the weight of the battery.

The conductive material may include polyacetylene, polyaniline,polypyrrole, polythiophene, polysulfurnitride, indium tin oxide (ITO),silver, palladium, nickel, etc. The conductive polymer may includepolyacetylene, polyaniline, polypyrrole, polythiophene,polysulfurnitride, etc. However, the non-conductive polymer used for thecurrent collector is not particularly limited to its kinds.

As mentioned above, when secondary batteries are subject to externalforces by bending or twisting, an electrode active material layer may bereleased from a current collector. For this reason, large amounts ofbinder components are used in the electrode active material layer so asto provide flexibility in electrodes. However, large amounts of bindermay be easily peeled off owing to swelling by an electrolyte solution,thereby deteriorating battery performances.

Accordingly, for the purpose of improving adhesiveness between anelectrode active material layer and a current collector, the innercurrent collector 120, 220 or the outer current collector 151 mayfurther comprise a primer coating layer consisting of a conductivematerial and a binder. The conductive material and the binder used inthe primer coating layer may be the same as those used in the formationof the conductive layer, which will be described below.

Further, referring to FIGS. 6 to 8, the outer current collector 151 maybe in the form of a mesh, and may have a plurality of recesses on atleast one surface thereof so as to more increase its surface area. Therecesses may be continuously patterned or intermittently patterned. Thatis, continuous patterned recesses may be formed with spacing apart witheach other in the longitudinal direction, or a plurality of holes may beformed in the form of intermittent patterns. The plurality of holes maybe a circular or polygonal shape. Furthermore, the inner currentcollector 120, 220 may have a plurality of recesses, similar to theouter current collector 151.

Such an outer current collector 151 may be made of stainless steel,aluminum, nickel, titanium, sintered carbon, or copper; stainless steeltreated with carbon, nickel, titanium or silver on the surface thereof;an aluminum-cadmium alloy; a non-conductive polymer treated with aconductive material on the surface thereof; a conductive polymer; ametal paste comprising metal powders of Ni, Al, Au, Ag, Pd/Ag, Cr, Ta,Cu, Ba or ITO; or a carbon paste comprising carbon powders of graphite,carbon black or carbon nanotube.

Meanwhile, the first supporting layer 154 may be a mesh-form porousmembrane or a non-woven fabric. Such a porous structure allows goodintroduction of an electrolyte solution in the outer electrode activematerial layer 152, and also the first supporting layer 154 itself hassuperior impregnation of the electrolyte solution to provide good ionicconductivity, thereby preventing an electrode resistance rise andeventually preventing the deterioration of battery performances.

The first supporting layer 154 may be made of any one selected from thegroup consisting of high-density polyethylene, low-density polyethylene,linear low-density polyethylene, ultra-high molecular weightpolyethylene, polypropylene, polyethylene terephthalate, polybutyleneterephthalate, polyester, polyacetal, polyamide, polycarbonate,polyimide, polyetheretherketone, polyethersulfone, polyphenylene oxide,polyphenylene sulfide, polyethylene naphthalate, and a mixture thereof.

Also, the first supporting layer 154 may further comprise a conductivematerial-coating layer having a conductive material and a binder on thetop surface thereof. The conductive material-coating layer functions toimprove the conductivity of an electrode active material layer andreduce electrode resistance, thereby preventing the deterioration ofbattery performances.

The conductive material and the binder used in the conductivematerial-coating layer may be the same as those used in the formation ofthe conductive layer, which will be described below.

Such conductive material-coating layer is more favorable when applied ina cathode because a cathode active material layer has low conductivityto intensify performance deterioration due to electrode resistance rise,than in an anode whose active material layer has relatively goodconductivity even in the absence of the conductive material-coatinglayer to exhibit performances similar to conventional anodes.

In the conductive material-coating layer, the conductive material andthe binder may be present in a weight ratio of 80:20 to 99:1. The use oflarge amounts of binder may induce a severe rise in electroderesistance. Therefore, when such a numerical range is satisfied,electrode resistance can be prevented from its severe rise. Also, asmentioned above, since the first supporting layer acts as a buffer whichcan prevent the release of an electrode active material layer, electrodeflexibility is not largely affected by the use of the binder in arelative small amount.

Meanwhile, the second supporting layer 155 may be a polymer film whichmay be made of any one selected from the group consisting of polyolefin,polyester, polyimide, polyamide and a mixture thereof.

The conductive layer 153 may be formed from a mixture of the conductivematerial and the binder in a weight ratio of 1:10 to 8:10.

Also, the conductive layer 155 may have a porous structure for goodintroduction of an electrolyte solution in an electrode active materiallayer, and have a pore size of 0.01 to 5 μm and a porosity of 5 to 70%.

The conductive material used in the conductive layer may comprise anyone selected from the group consisting of carbon black, acetylene black,ketjen black, carbon fiber, carbon nanotube, graphene and a mixturethereof.

The binder used in the conductive layer may be selected from the groupconsisting of polyvinylidene fluoride (PVDF), polyvinylidenefluoride-co-hexafluoro propylene, polyvinylidenefluoride-co-trichloroethylene, polybutyl acrylate, polymethylmethacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinylacetate,polyethylene-co-vinyl acetate, polyethylene oxide, polyarylate,cellulose acetate, cellulose acetate butyrate, cellulose acetatepropionate, cyanoethylpullulan, cyanoethylpolyvinylalcohol,cyanoethylcellulose, cyanoethylsucrose, pullulan, carboxyl methylcellulose, styrene-butadiene rubber, acrylonitrile-styrene-butadienecopolymer, polyimide and a mixture thereof.

Meanwhile, the core 110, 210 for supplying lithium ions comprises anelectrolyte which is not particularly limited to its kinds and may beselected from a non-aqueous electrolyte solution using ethylenecarbonate (EC), propylene carbonate (PC), butylenes carbonate (BC),vinylene carbonate (VC), diethyl carbonate (DEC), dimethyl carbonate(DMC), ethyl methyl carbonate (EMC), methyl formate (MF),γ-butyrolactone (γ-BL), sulfolane, methyl acetate (MA) or methylpropionate (MP); a gel polymer electrolyte using PEO, PVdF, PVdF-HFP,PMMA, PAN, or PVAc; and a solid electrolyte using PEO, polypropyleneoxide (PPO), polyether imine (PEI), polyethylene sulphide (PES), orpolyvinyl acetate (PVAc). Also, the electrolyte may further comprise alithium salt which may be selected from LiCl, LiBr, LiI, LiClO₄, LiBF₄,LiB₁₀Cl₁₀, LiPF₆, LiCF₃SO₃, LiCF₃CO₂, LiAsF₆, LiSbF₆, LiAlCl₄, CH₃SO₃Li,CF₃SO₃Li, (CF₃SO₂)₂NLi, lithium chloroborate, lower aliphatic lithiumcarbonate, lithium tetraphenylborate, and a mixture thereof. The core110, 210 for supplying lithium ions may consist of only an electrolyte,and especially a liquid electrolyte may be formed by using a porouscarrier.

In the present disclosure, the inner electrode may be an anode or acathode, and the outer electrode may be a cathode or an anodecorresponding to the inner electrode.

The electrode active material layers of the present disclosure allowions to move through the current collector, and the movement of ions iscaused by the interaction of ions such as intercalation/deintercalationof ions into and from the electrolyte layer.

Such electrode active material layers may be divided into an anodeactive material layer and a cathode active material layer.

Specifically, when the inner electrode is an anode and the outerelectrode is a cathode, the inner electrode active material layer maycomprise an anode active material selected from the group consisting ofnatural graphite, artificial graphite, or carbonaceous material;lithium-titanium complex oxide (LTO), and metals (Me) including Si, Sn,Li, Zn, Mg, Cd, Ce, Ni and Fe; alloys of the metals; an oxide (MeOx) ofthe metals; a complex of the metals and carbon; and a mixture thereof,and the outer electrode active material layer may comprise a cathodeactive material selected from the group consisting of LiCoO₂, LiNiO₂,LiMn₂O₄, LiCoPO₄, LiFePO₄, LiNiMnCoO₂,LiNi_(1-x-y-z)Co_(x)M1_(y)M2_(z)O₂ (wherein M1 and M2 are eachindependently selected from the group consisting of Al, Ni, Co, Fe, Mn,V, Cr, Ti, W, Ta, Mg and Mo, and x, y and z are each independently anatomic fraction of oxide-forming elements, in which 0≦x<0.5, 0≦y<0.5,0≦z<0.5, and x+y+z≦1), and a mixture thereof.

Alternatively, when the inner electrode is a cathode and the outerelectrode is an anode, the inner electrode active material layer becomesa cathode active material layer and the outer electrode active materiallayer becomes an anode active material layer.

An electrode active material layer generally comprises an electrodeactive material, a binder and a conductive material and is combined witha current collector to construct an electrode. When the electrode issubject to deformation, e.g., folding or severe bending by externalforces, the electrode active material layer is released, therebydeteriorating battery performances and battery capacity. In contrast, inan electrode comprising the wound sheet-form outer current collector ofthe present disclosure, such a deformation is less induced because thesheet-form outer current collector being spirally wound has elasticityto disperse the external forces applied in the electrode. From this, therelease of an active material can be prevented.

In the present disclosure, the separation layer may be an electrolytelayer or a separator.

The electrolyte layer serving as an ion channel may be made of agel-type polymer electrolyte using PEO, PVdF, PVdF-HFP, PMMA, PAN orPVAC, or a solid electrolyte using PEO, polypropylene oxide (PPO),polyethylene imine (PEI), polyethylene sulfide (PES) or polyvinylacetate (PVAc). The matrix of the solid electrolyte is preferably formedusing a polymer or a ceramic glass as the backbone. In the case oftypical polymer electrolytes, the ions move very slowly in terms ofreaction rate, even when the ionic conductivity is satisfied. Thus, thegel-type polymer electrolyte which facilitates the movement of ions ispreferably used compared to the solid electrolyte. The gel-type polymerelectrolyte has poor mechanical properties and thus may comprise asupport to improve poor mechanical properties, and the support may be aporous-structured support or a cross-linked polymer. The electrolytelayer of the present invention can serve as a separator, and thus anadditional separator may be omitted.

In the present disclosure, the electrolyte layer may further comprise alithium salt. The lithium salt can improve an ionic conductivity andresponse time. Non-limiting examples of the lithium salt may includeLiCl, LiBr, LiI, LiClO₄, LiBF₄, LiB₁₀Cl₁₀, LiPF₆, LiCF₃SO₃, LiCF₃CO₂,LiAsF₆, LiSbF₆, LiAlCl₄, CH₃SO₃Li, CF₃SO₃Li, (CF₃SO₂)₂NLi, lithiumchloroborate, lower aliphatic lithium carbonate, and lithiumtetraphenylborate.

Examples of the separator may include, but is not limited to, a porouspolymer substrate made of a polyolefin-based polymer selected from thegroup consisting of ethylene homopolymers, propylene homopolymers,ethylene-butene copolymers, ethylene-hexene copolymers, andethylene-methacrylate copolymers; a porous polymer substrate made of apolymer selected from the group consisting of polyesters, polyacetals,polyamides, polycarbonates, polyimides, polyether ether ketones,polyether sulfones, polyphenylene oxides, polyphenylene sulfides andpolyethylene naphthalates; a porous substrate made of a mixture ofinorganic particles and a binder polymer; or a separator having a porouscoating layer formed on at least one surface of the porous polymersubstrate and comprising inorganic particles and a binder polymer.

In the porous coating layer formed from inorganic particles and a binderpolymer, the inorganic particles are bound to each other by the binderpolymer (i.e., the binder polymer connects and immobilizes the inorganicparticles), and also the porous coating layer maintains the state ofbinding with the first supporting layer by the binder polymer, In such aporous coating layer, the inorganic particles are filled in contact witheach other, from which interstitial volumes are formed between theinorganic particles. The interstitial volumes between the inorganicparticles become empty spaces to form pores.

Among these, in order for the lithium ions of the core for supplyinglithium ions to be transferred to the outer electrode, it is preferredto use a non-woven fabric separator corresponding to the porous polymersubstrate made of a polymer selected from the group consisting ofpolyesters, polyacetals, polyamides, polycarbonates, polyimides,polyether ether ketones, polyether sulfones, polyphenylene oxides,polyphenylene sulfides and polyethylene naphthalates.

Also, the cable-type secondary battery of the present disclosure has aprotection coating 160, 260. The protection coating acts as an insulatorand is formed to surround the outer current collector, therebyprotecting the electrodes against moisture in the air and externalimpacts. The protection coating 160, 260 may be made of conventionalpolymer resins having a moisture-blocking layer. The moisture-blockinglayer may be made of aluminum or a liquid-crystalline polymer which havegood water-blocking ability, and the polymer resins may be PET, PVC,HDPE or epoxy resins.

Hereinafter, the preparation of a cable-type secondary battery accordingto one embodiment of the present invention will be briefly explainedwith reference to FIGS. 3 and 9.

First, a wire-form inner current collector 120 having an inner electrodeactive material layer 130 formed on a surface thereof is wound to obtaina hollow inner electrode whose central part is empty.

The formation of inner electrode active material layer 130 on a surfaceof the wire-form inner current collector 120 may be made by conventionalcoating methods, for example, by an electroplating process or an anodicoxidation process. Also, in order to maintain constant intervals, it ispreferable to carry out coating methods in which an electrode slurrycontaining an active material is applied through a comma coater or aslot die coater. In addition, the electrode slurry containing an activematerial may be applied by way of dip coating or extrusion-coating usingan extruder.

Subsequently, a sheet-form separation layer 130 for preventing a shortcircuit between electrodes is wound on a surface of the inner electrode.

Next, an outer electrode is obtained in the form of a sheet by thefollowing procedures.

Specifically, a sheet-form outer current collector is provided and asecond supporting layer is formed by compression on one surface of thesheet-form outer current collector (S1); a slurry containing an outerelectrode active material is applied on another surface of thesheet-form outer current collector, followed by drying, to form an outerelectrode active material layer (S2); a slurry containing a conductivematerial and a binder is applied on the outer electrode active materiallayer, and then a first porous supporting layer is placed thereon (S3);the resultant obtained in step (S3) is compressed to form a conductivelayer which is adhered between the outer electrode active material layerand the first porous supporting layer to be integrated with each other,thereby obtaining an outer electrode in the form of a sheet.

Then, the sheet-form outer electrode 150 is spirally wound on the outersurface of the separation layer 140 to obtain an electrode assembly, asshown in FIG. 9.

Next, a protection coating 160 is formed to surround the outer surfaceof the electrode assembly.

The protection coating 160 acting as an insulator is formed on theoutermost so as to protect the electrode against moisture in the air andexternal impact. The protection coating 160 may be made of a polymerresin having a moisture-blocking layer as mentioned above.

Then, an electrolyte is introduced in the empty space formed in thecenter of the inner electrode, to form a core 110 for supplying lithiumions.

Thus, the core 110 for supplying lithium ions may be formed by carryingout the introduction of an electrolyte solution after the protectioncoating 160 is formed on the outer surface of the electrode assembly.Also, the core 110 may be formed in a wire form by introducing a polymerelectrolyte using an extruder before forming the wound wire-form innerelectrode, may be formed by providing a wire-form carrier made of asponge material and introducing a non-aqueous electrolyte solutiontherein, or may be formed by introducing a non-aqueous electrolytesolution in the empty space of the inner electrode center afterproviding the inner electrode.

Finally, the introduction part of the electrolyte solution is completelysealed to prepare a cable-type secondary battery.

Hereinafter, another embodiment of the present disclosure will bedescribed.

A cable-type secondary battery according to another embodiment of thepresent disclosure comprises an inner electrode; a separation layersurrounding the outer surface of the inner electrode to prevent a shortcircuit between electrodes; and a sheet-form outer electrode surroundingthe outer surface of the separation layer and formed by being spirallywound.

Furthermore, referring to FIG. 10, a cable-type secondary battery 300according to one embodiment of the present invention comprises two ormore cores 310 for supplying lithium ions, which comprise anelectrolyte; two or more inner electrodes arranged in parallel to eachother, each inner electrode comprising one or more wire-form innercurrent collector 320 which is wound to surround the outer surface ofeach core 310 for supplying lithium ions, and an inner electrode activematerial layer 330 formed on a surface of the wire-form inner currentcollector 320; a separation layer 340 surrounding the outer surface ofthe inner electrodes to prevent a short circuit between electrodes; andan outer electrode surrounding the outer surface of the separationlayer, wherein the outer electrode 350 is in the form of a sheet whichcomprises an outer current collector 351, an outer electrode activematerial layer 352 formed on one surface of the outer current collector351, a conductive layer 353 formed on the outer electrode activematerial layer 352 and comprising a conductive material and a binder, afirst porous supporting layer 354 formed on the conductive layer 353,and a second supporting layer 355 formed on another surface of the outercurrent collector 351.

The outer electrode may be spirally wound to surround the separationlayer.

In the cable-type secondary battery 300 which has a plurality of innerelectrodes, the number of the inner electrodes can be adjusted tocontrol the loading amount of the electrode active material layers aswell as battery capacity, and a probability of short circuit can beprevented owing to the presence of multiple electrodes.

Hereinafter, the present invention will be described in detail throughspecific examples. However, the description proposed herein is just apreferable example for the purpose of illustrations only, not intendedto limit the scope of the invention, so it should be understood that theexamples are provided for a more definite explanation to an ordinaryperson skilled in the art.

EXAMPLE 1

75 wt % of Graphite as an anode active material, 5 wt % of Denka blackas a conductive material and 25 wt % of PVdF as a binder were mixed toobtain an anode active material-containing slurry. The slurry was coatedon the outer surface of a wire-form Cu current collector having adiameter of 250 μm, to obtain a wire-form inner electrode having ananode active material layer.

Four wire-form inner electrodes obtained above were spirally wound sothat they are crossed with each other, to prepare a spring-type innerelectrode whose center is empty, so a core for supplying lithium ionscan be inserted therein.

Then, a separator sheet was wound to surround the outer surface of theinner electrode to form a separation layer.

Meanwhile, a sheet of aluminum foil was used as a current collector, anda polyethylene film was compressed on one surface of the sheet, to forma second supporting layer.

Next, another surface of the sheet was coated with a cathode activematerial-containing slurry obtained by dispersing 80 wt % of LiCoO₂ as acathode active material, 5 wt % of Denka black as a conductive materialand 15 wt % of PVdF as a binder in NMP used as a solvent, followed bydrying, to form a cathode active material layer.

Subsequently, a conductive material-containing slurry obtained by mixingDenka black and PVdF in a weight ratio of 40:60 was coated on the top ofthe cathode active material layer, and then a PET non-woven fabric to bea first supporting layer was placed on the coating, followed bycompression, to obtain a laminate having the second supporting layer,the current collector, the cathode active material layer, a layer of theconductive material-containing slurry and the first supporting layer inorder. The laminate obtained after compression was cut into a piecehaving a width of 2 mm, to prepare a sheet-form cathode for secondarybatteries.

Then, the sheet-form cathode was spirally wound on the outer surface ofthe separation layer, to prepare an electrode assembly.

On the outer surface of the electrode assembly, a heat-shrinkable tubehaving a moisture-blocking layer was applied and contracted with heat,to form a protection coating layer.

Then, a non-aqueous electrolyte solution (1M LiPF₆, EC:PC:DEC=1:1:1(volume ratio)) was introduced in the center of the inner electrodeusing a syringe, to form a core for supplying lithium ions, followed bycompletely sealing. Thereby, a cable-type secondary battery wasprepared.

EXAMPLE 2

The procedures of Example 1 were repeated except that a mixture ofPVdF-HFP(5%) in 10:90 (wt/wt) was coated on the inner electrode tofurther form a polymer supporting layer, thereby preparing a cable-typesecondary battery.

Comparative Example

The procedures of Example 1 were repeated except that a wire-form Alcurrent collector was wound on the outer surface of the separationlayer, and the outer surface of the wound wire-form current collectorwas coated with a cathode active material-containing slurry obtained bydispersing 80 wt % of LiCoO₂ as a cathode active material, 5 wt % ofDenka black as a conductive material and 15 wt % of PVdF as a binder inNMP used as a solvent, followed by drying, to form a cathode activematerial layer, thereby preparing a cable-type secondary battery.

Evaluation of Battery Performances

For the cable-type secondary batteries prepared in Example 1 and theComparative Example, 100 cycles of charge/discharge processes werecarried out with a current density of 0.3 C at a voltage condition of4.2 to 2.5 V. The change of battery capacity was measured with thecurrent density being varied, and the results thereof are shown in FIGS.11 and 12.

As shown in FIGS. 11 and 12, the battery of Example 1 exhibitedsurprisingly improved cycle characteristic and rate characteristic dueto its advantage in terms of resistance, as compared with that of theComparative Example.

Bending Test for Evaluating Battery Flexibility

In order to confirm the flexibility of the cable-type secondary batteryprepared in Example 1, the battery was fixed between grips of a tensiletester, and then the procedure of bending and spreading the battery wasrepeated with varying a distance between the grips in the range of from1 to 6 cm at a speed of 500 mm/min. In this procedure, in order toconfirm a substantial flexibility of the battery, both ends of thebattery were each connected with (+) and (−) terminals of a charge anddischarge regulator and discharging was carried out with a currentdensity of 0.1 C.

FIG. 13 shows a discharge profile over time, which from the battery ofExample 1 was confirmed to exhibit stable performances as time passed.

APPLICABILITY TO THE INDUSTRY

The present disclosure has been described in detail. However, it shouldbe understood that the detailed description and specific examples, whileindicating preferred embodiments of the disclosure, are given by way ofillustration only, since various changes and modifications within thespirit and scope of the disclosure will become apparent to those skilledin the art from this detailed description.

What is claimed is:
 1. A cable-type secondary battery, comprising: aninner electrode; a separation layer surrounding the outer surface of theinner electrode to prevent a short circuit between electrodes; and asheet-form outer electrode spirally wound to surround the separationlayer or the inner electrode, wherein the inner electrode has a hollowstructure whose central part is empty.
 2. The cable-type secondarybattery according to claim 1, wherein the inner electrode comprises oneor more wire-form inner current collectors being spirally wound or oneor more sheet-form inner current collectors being spirally wound.
 3. Thecable-type secondary battery according to claim 1, wherein the innerelectrode comprises two or more wire-form inner current collectors beingspirally crossed with each other.
 4. The cable-type secondary batteryaccording to claim 1, wherein the inner electrode is provided with acore of inner current collector, a core for supplying lithium ions,which comprises an electrolyte, or a filling core therein.
 5. Thecable-type secondary battery according to claim 4, wherein the core ofinner current collector is made of carbon nanotube, stainless steel,aluminum, nickel, titanium, sintered carbon, or copper; stainless steeltreated with carbon, nickel, titanium or silver on the surface thereof;an aluminum-cadmium alloy; a non-conductive polymer treated with aconductive material on the surface thereof; a conductive polymer.
 6. Thecable-type secondary battery according to claim 4, wherein the core forsupplying lithium ions comprises a gel polymer electrolyte and asupport.
 7. The cable-type secondary battery according to claim 4,wherein the core for supplying lithium ions comprises a liquidelectrolyte and a porous carrier.
 8. The cable-type secondary batteryaccording to claim 4, wherein the electrolyte is selected from anon-aqueous electrolyte solution using ethylene carbonate (EC),propylene carbonate (PC), butylenes carbonate (BC), vinylene carbonate(VC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methylcarbonate (EMC), methyl formate (MF), γ-butyrolactone (γ-BL), sulfolane,methyl acetate (MA) or methyl propionate (MP); a gel polymer electrolyteusing PEO, PVdF, PVdF-HFP, PMMA, PAN, or PVAc; and a solid electrolyteusing PEO, polypropylene oxide (PPO), polyether imine (PEI),polyethylene sulphide (PES), or polyvinyl acetate (PVAc).
 9. Thecable-type secondary battery according to claim 4, wherein theelectrolyte further comprises a lithium salt.
 10. The cable-typesecondary battery according to claim 9, wherein the lithium salt isselected from LiCl, LiBr, LiI, LiClO₄, LiBF₄, LiB₁₀Cl₁₀, LiPF₆,LiCF₃SO₃, LiCF₃CO₂, LiAsF₆, LiSbF₆, LiAlCl₄, CH₃SO₃Li, CF₃SO₃Li,(CF₃SO₂)₂NLi, lithium chloroborate, lower aliphatic lithium carbonate,lithium tetraphenylborate, and a mixture thereof.
 11. The cable-typesecondary battery according to claim 4, the filling core is made ofpolymer resins, rubber and inorganics in the form of a wire, a fiber, apowder, a mesh and a foam.
 12. A cable-type secondary battery,comprising: an inner electrode; a separation layer surrounding the outersurface of the inner electrode to prevent a short circuit betweenelectrodes; and a sheet-form outer electrode spirally wound to surroundthe separation layer or the inner electrode, wherein the separationlayer is an electrolyte layer or a separator.
 13. The cable-typesecondary battery according to claim 12, wherein the electrolyte layercomprises an electrolyte selected from a gel polymer electrolyte usingPEO, PVdF, PMMA, PVdF-HFP, PAN, or PVAc; and a solid electrolyte usingPEO, polypropylene oxide (PPO), polyether imine (PEI), polyethylenesulphide (PES), or polyvinyl acetate (PVAc).
 14. The cable-typesecondary battery according to claim 12, wherein the electrolyte layerfurther comprises a lithium salt.
 15. The cable-type secondary batteryaccording to claim 14, wherein the lithium salt is selected from thegroup consisting of LiCl, LiBr, LiI, LiClO₄, LiBF₄, LiB₁₀Cl₁₀, LiPF₆,LiCF₃SO₃, LiCF₃CO₂, LiAsF₆, LiSbF₆, LiAlCl₄, CH₃SO₃Li, CF₃SO₃Li,(CF₃SO₂)₂NLi, lithium chloroborate, lower aliphatic lithium carbonate,lithium tetraphenylborate, and a mixture thereof.
 16. The cable-typesecondary battery according to claim 12, wherein the separator is aporous polymer substrate made of a polyolefin-based polymer selectedfrom the group consisting of ethylene homopolymers, propylenehomopolymers, ethylene-butene copolymers, ethylene-hexene copolymers,and ethylene-methacrylate copolymers; a porous polymer substrate made ofa polymer selected from the group consisting of polyesters, polyacetals,polyamides, polycarbonates, polyimides, polyether ether ketones,polyether sulfones, polyphenylene oxides, polyphenylene sulfides andpolyethylene naphthalates; a porous substrate made of a mixture ofinorganic particles and a binder polymer; or a separator having a porouscoating layer formed on at least one surface of the porous polymersubstrate and comprising inorganic particles and a binder polymer. 17.The cable-type secondary battery according to claim 16, wherein theporous polymer substrate is a porous polymer film substrate or a porousnon-woven fabric substrate.
 18. A cable-type secondary battery,comprising: a core for supplying lithium ions, which comprise anelectrolyte; an inner electrode comprising one or more wire-form innercurrent collector which is wound to surround the outer surface of thecore for supplying lithium ions, and an inner electrode active materiallayer formed on a surface of the wire-form inner current collector; aseparation layer surrounding the outer surface of the inner electrodesto prevent a short circuit between electrodes; and a sheet-form outerelectrode surrounding the outer surface of the separation layer, whereinthe outer electrode comprises an outer current collector, an outerelectrode active material layer formed on one surface of the outercurrent collector, a conductive layer formed on the outer electrodeactive material layer and comprising a conductive material and a binder,a first porous supporting layer formed on the conductive layer, and asecond supporting layer formed on another surface of the outer currentcollector.
 19. The cable-type secondary battery according to claim 18,wherein the outer electrode is spirally wound to surround the separationlayer.
 20. A cable-type secondary battery, comprising: two or more coresfor supplying lithium ions, which comprise an electrolyte; two or moreinner electrodes arranged in parallel to each other, each innerelectrode comprising one or more wire-form inner current collector whichis wound to surround the outer surface of each core for supplyinglithium ions, and an inner electrode active material layer formed on asurface of the wire-form inner current collector; a separation layersurrounding the outer surface of the inner electrodes to prevent a shortcircuit between electrodes; and a sheet-form outer electrode surroundingthe outer surface of the separation layer, wherein the outer electrodecomprises an outer current collector, an outer electrode active materiallayer formed on one surface of the outer current collector, a conductivelayer formed on the outer electrode active material layer and comprisinga conductive material and a binder, a first porous supporting layerformed on the conductive layer, and a second supporting layer formed onanother surface of the outer current collector.
 21. The cable-typesecondary battery according to claim 20, wherein the outer electrode isspirally wound to surround the separation layer.
 22. The cable-typesecondary battery according to claim 20, wherein the inner electrodecomprise one or more wire-form inner current collectors being spirallywound, or one or more sheet-form inner current collectors being spirallywound.